EP2001952B1 - Bonding agents and sealants based on liquid rubbers - Google Patents
Bonding agents and sealants based on liquid rubbers Download PDFInfo
- Publication number
- EP2001952B1 EP2001952B1 EP07711401A EP07711401A EP2001952B1 EP 2001952 B1 EP2001952 B1 EP 2001952B1 EP 07711401 A EP07711401 A EP 07711401A EP 07711401 A EP07711401 A EP 07711401A EP 2001952 B1 EP2001952 B1 EP 2001952B1
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- EP
- European Patent Office
- Prior art keywords
- preference
- composition according
- rubber
- curing
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000007788 liquid Substances 0.000 title claims abstract description 42
- 239000000565 sealant Substances 0.000 title claims abstract description 15
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- 239000007767 bonding agent Substances 0.000 title 1
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- 239000011593 sulfur Substances 0.000 claims abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 19
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- 150000004053 quinones Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012215 seam sealant Substances 0.000 description 1
- 150000003349 semicarbazides Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- RVEZZJVBDQCTEF-UHFFFAOYSA-N sulfenic acid Chemical compound SO RVEZZJVBDQCTEF-UHFFFAOYSA-N 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical class CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical class [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L13/00—Compositions of rubbers containing carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D107/00—Coating compositions based on natural rubber
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J121/00—Adhesives based on unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
- C08L2666/08—Homopolymers or copolymers according to C08L7/00 - C08L21/00; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
Definitions
- the present invention relates to a one-component, hot-curing reactive composition based on natural and / or synthetic olefinic double bonds containing elastomers and vulcanizing agents and their use as one-component adhesive, sealant, sealant or coating composition in vehicle construction, especially in automotive body.
- hot-curing, reactive adhesives for Bördeinahtverklebungen or overlapping bonds in the shell on oiled sheet applied and joined.
- the curing of the adhesives or sealants used in this case takes place later in the paint drying ovens.
- the bonded or sealed or sealed parts undergo cleaning, phosphating and dipping priming steps.
- the treatment agents used in these stages can be used to rinse the adhesives or sealants from the adhesive joints.
- the adhesive, sealant or sealant is used by means of precuring mechanisms, such as induction heating, Shell furnaces, pre-hardened or rheologically adjusted infrared emitters to survive the subsequent pretreatment without being washed out.
- welding points can be used to reinforce the body parts.
- the curing of the adhesives takes place when passing through the subsequent paint ovens (for the cathodic dip paint (KTL), filler, topcoat, etc.).
- Epoxy resin compositions which contain an epoxy adduct of a carboxyl group-containing copolymers based on butadiene-acrylonitrile or similar butadiene copolymers and a reaction product of an epoxy resin-soluble or dispersible elastomeric prepolymers having terminal isocyanate groups with a polyphenol or aminophenol and subsequent reaction of this adduct with a epoxy resin.
- these compositions may contain one or more epoxy resins.
- amino-functional curing agents, polyaminoamides, polyphenols, polycarboxylic acids and their anhydrides or catalytic curing agents and optionally accelerators are proposed. It is stated that these compositions are suitable as adhesives which, depending on the concrete composition, may have high strength, high glass transition temperature, high peel strength, high impact resistance or high crack propagation resistance.
- the EP-A-338985 describes modified epoxy resins containing a liquid copolymer based on butadiene, a polar, ethylenically unsaturated comonomer and optionally other ethylenically unsaturated comonomers and further a reaction product of dihydroxy-terminated or diaminotermin faced polyalkylene glycols and diisocyanates and a monophenol, a mercaptoalcohol or an aliphatic lactam , According to the teaching of this document, these compositions can be used for the flexibilization of epoxy resins. In addition to the aforementioned ingredients, these compositions are still Epoxy resins and a hardener or accelerator included. Such mixtures should be used as adhesives, adhesive films, patches, matrix resins, paints or sealants.
- the WO01 / 94492 describes condensation products of cyclic carboxylic anhydrides of dicarboxylic acids, tricarboxylic anhydrides or tetracarboxylic anhydrides and difunctional polyamines, in particular polyoxyalkyleneamines as structural components for epoxy resin compositions.
- the condensation products based on tricarboxylic anhydrides or tetracarboxylic anhydrides are distinguished on average by more than one imide group and carboxyl group per molecule. Possibly.
- Condensation products of tri- or polyfunctional polyols and / or tri- or polyfunctional amino-terminated polymers and cyclic carboxylic anhydrides can also be present in the compositions.
- these compositions contain conventional rubber-modified epoxy resins and liquid and / or solid polyepoxide resins and conventional hardeners and accelerators and optionally fillers and rheology aids. It is proposed to use these modified epoxy resin compositions as impact-resistant, impact peel-resistant and peel-resistant adhesives in vehicle construction and in electronics, in particular because they have very good impact and peel properties at very low temperatures and should ensure a very good corrosion resistance and aging resistance of the bond.
- JP 2000-313786 A describes an impact-resistant acrylic resin composition
- component B should be present as a particulate material having an average particle size of 0.2 to 10 .mu.m as a disperse phase, that having a continuous phase
- the component A is surrounded.
- the ratio of the volume of component A to the volume of component B should be 0.5 to 4 and at least a portion of component A should be chemically bound to a portion of component B. It It is stated that these resin compositions should have an improved impact resistance with at the same time good aging resistance.
- JP 2000-319475 A an impact resistant resin composition of a (meth) acrylate copolymer component A and a modified polyurethane elastomer component B.
- the polyurethane elastomer component B is to be present as a discontinuous dispersed phase in the continuous phase A, wherein the disperse phase has a structure containing a Has microphase separation.
- at least part of component A should be chemically bound to a part of component B.
- EP 0270318 A2 describes a modified composition for use as a structural adhesive. These adhesive compositions contain a liquid rubber with olefinically unsaturated end groups, which has been reacted with a monoisocyanate component. It is proposed, for the preparation of these liquid elastomers, to react carboxyl-terminated polybutadiene or a polybutadiene-acrylonitrile or polybutadiene-methacrylonitrile-styrene copolymer with glycidyl methacrylate and then to react the resulting secondary hydroxyl groups with monoisocyanate compounds.
- Such modified olefinic end-group liquid elastomers are then mixed with olefinically unsaturated monomers selected from acrylic acid esters, acrylic acid, styrene, substituted styrene, and free radical initiators to provide a room temperature curable structural adhesive. It is stated that such adhesive compositions have improved aging resistance and improved low temperature properties as compared to other acrylate-based structural adhesives.
- WO 02/070619 describes elastic (meth) acrylate adhesive compositions having high elongation at break.
- the adhesive compositions should have at least one monofunctional (meth) acrylate monomer A whose homopolymer or copolymer has a glass transition temperature between 40 ° C and 140 ° C.
- the composition should contain a monofunctional (meth) acrylate monomer B having the following structure:
- R is hydrogen or a methyl group
- R ' is hydrogen or C 1 to C 3 -alkyl, in particular hydrogen or ethyl and R "is a C 3 -C 20 -alkyl group or a phenoxy group or an alkoxy group an elastomer having a molecular weight range between 1000 and 9000 with (meth) acrylate groups in the composition is present
- the compositions disclosed therein are particularly suitable for bonding materials having different thermal expansion coefficients, as described, for example, in US Pat
- the adhesion of side panels of trailers or direct glazing is mentioned by way of example: it is stated that these compositions have a very high impact strength at low temperatures.
- the WO 96/23040 describes one-component, heat-curing structural adhesives based on liquid rubbers, which may optionally contain functional groups, solid rubbers, thermoplastic polymer powders and sulfur, and vulcanization accelerators. These adhesives are suitable for bonding metal parts. Tensile shear strengths of over 15 MPa and high elongation at break of more than 15% can be obtained. These adhesives are essentially free of low molecular weight epoxy resins and are particularly suitable for use in carcass construction in the automotive industry.
- WO99 / 03946 From the WO99 / 03946 are heat-pumpable, heat-curing compositions based on ethylene-vinyl acetate copolymers (EVA), containing at least one solid EVA copolymer with a softening point above 50 ° C, measured by the Ring & Ball method according to ASTM D 28, at least one liquid reactive Plasticizers having olefinically unsaturated double bonds and at least one peroxidic crosslinking agent known.
- EVA ethylene-vinyl acetate copolymers
- these compositions are suitable as sealants of fine and coarse seams in vehicle construction. If blowing agents are added, they can also be used as relining adhesives.
- the preferred applications are in the shell in the manufacture of automobiles.
- WO02 / 4825 discloses heat-curing, reactive compositions based on natural and / or synthetic olefinic double bonds elastomers based on liquid polyenes, and optionally solid rubbers.
- the vulcanization system consists of sulfur and / or metal oxides and one or more organic accelerators containing one or more heterocyclic compound (s) having at least 2 nitrogen atoms in the ring. These compositions can be vulcanized while avoiding or greatly reducing the odor nuisance of sulfur and sulfur compounds. It is stated that these compositions are known as Adhesives, sealants or coating compositions, especially in the automotive industry.
- thermosetting reactive compositions based on natural and / or synthetic olefinic double bonds containing liquid elastomers and vulcanizing agents, which in addition to conventional liquid polyenes at least one liquid cis-1,4-polyisoprene having a molecular weight between 20,000 and 70,000 and a vulcanization from Sulfur, accelerators and quinone oximes are known.
- These adhesives exhibit a plastisol-like flow behavior, so that they can be applied at room temperature with conventional spray systems. It is stated that these compositions are useful as seam sealants and sealants, as underbonding adhesives, as well as structural adhesives, e.g. B. should be suitable as Bördelnahtklebstoff.
- the high-strength adhesives of the abovementioned state of the art based on rubber require improvement in their properties at low temperatures; they have no elastic and impact-resistant properties, especially at low temperatures, since they embrittle too much at low temperatures, presumably because of the high degree of crosslinking.
- the object of the present invention was therefore to provide high-strength and impact-resistant adhesives which can be used for automotive OEM applications and which do not contain epoxy resins or (meth) acrylate resins as an essential component without the use of expensive specialty polymers or copolymers.
- liquid is meant “liquid at room temperature (22 ° C)”.
- Another object of the present invention is the use of the above-mentioned hot-curing, reactive compositions as a one-component adhesive, sealant or coating composition or sealant in automotive body.
- liquid polyene (s) or elastomers a) contain at least one olefinically unsaturated double bond per molecule. They can be selected from the following group of homopolymers and / or copolymers:
- Polybutadienes in particular the 1,3- and 1,2-poly-butadienes, polybutenes, polyisobutylenes, 1,4- and 3,4-polyisoprenes, styrene-butadiene copolymers.
- Butadiene-acrylonitrile copolymers wherein one or more of these polymers may have terminal and / or (randomly distributed) pendant functional groups. Examples of such functional groups are hydroxy, amino, carboxyl, carboxylic anhydride or epoxy groups.
- the molecular weight of these liquid rubbers is typically below 80,000 and above 400, preferably between 800 and 25,000.
- the proportion of liquid rubber in the overall composition depends on the desired rheology of the uncured composition and the desired mechanical stiffness or strength of the composite and, if applicable acoustic damping properties of the cured composition from.
- the proportion of liquid rubber or elastomer normally varies between 2 and 55% by weight of the total formulation. It has proven to be expedient, preferably mixtures of liquid rubbers of different Molecular weights and different configuration with respect to the remaining double bonds.
- both block copolymers and those with random distribution of the comonomers can be used as copolymers.
- a liquid rubber component having hydroxyl groups, carboxyl groups or acid anhydride groups is proportionately used in the particularly preferred formulations.
- the proportion of carboxyl group-containing liquid rubber may be from 0 to 25% by weight, preferably from 1 to 15 and very particularly preferably from 3 to 10% by weight.
- liquid polybutadienes preferably having a narrow molecular weight distribution, which can be prepared by anionic polymerization.
- These low molecular weight liquid polybutadienes contain three structural types in the polymer chain: vinylic 1,2-double bonds, cis 1,4-double bonds and trans 1,4-double bonds, these liquid polymers having 10 to 20% vinylic 1,2-double bonds, 50 to 60 have% trans 1,4 double bonds and 25 to 35% cis 1,4 double bonds in their microstructure.
- the molecular weights of these liquid butadienes are between 2,000 and 12,000, preferably between 5,000 and 9,000 (number average molecular weight).
- the adhesive composition of the invention may also contain a proportion of solid rubbers.
- suitable rubbers are polybutadiene, preferably with a very high proportion of cis-1,4-double bonds (typically over 95%), styrene-butadiene rubber, butadiene-acrylonitrile rubber, synthetic or natural isoprene rubber, polycyclooctenamer, butyl rubber or polyurethane rubber ,
- the proportion of solid rubber may be up to 15% by weight, preferably between 0 and 12% by weight and very particularly preferably between 0 and 9% by weight.
- the one-component, hot-curing reactive compositions according to the invention comprise a vulcanization system of sulfur and accelerators and / or optionally quinone oximes.
- vulcanizing agents are suitable in combination with elemental sulfur, but also vulcanization systems without free sulfur.
- the latter include the vulcanization systems based on thiuram disulfides, organic peroxides, polyfunctional amines, quinones, p-benzoquinone dioxime, p-nitrosobenzene and dinitrosobenzene, or crosslinking with (blocked) diisocyanates.
- vulcanization systems based on elemental sulfur and organic vulcanization accelerators and zinc compounds.
- the powdered sulfur is used in amounts of 4 to 25 wt.%, Based on the total composition, more preferably amounts are used between 5 and 15 wt.%.
- Suitable organic accelerators are dithiocarbamates (in the form of their ammonium or metal salts), xanthates, thiuram compounds (monosulfides and disulfides), thiazole compounds, aldehyde / amine accelerators (eg hexamethylenetetramine) and guanidine accelerators, very particular preference is given to dibenzothiazyl disulfide (MBTS), 2 Mercaptobenzothiazole (MBT), its zinc salt (ZMBT), zinc dibenzyldithiocarbamate (ZBEC), N-cyclohexylbenzodithiazyl sulfenamide (CBS) or diphenylguanidine.
- MBTS dibenzothiazyl disulfide
- MTT 2 Mercaptobenzothiazole
- ZMBT zinc salt
- ZBEC zinc dibenzyldithiocarbamate
- CBS N-cyclohexylbenzodithia
- the accelerators are used in amounts between 0.25 and 8.0 wt.%, Particularly preferably between 0.4 and 6 wt.%.
- the vulcanization mixture may also contain bifunctional crosslinkers.
- specific examples are crosslinkers based on bifunctional dithiocarbamates such as 1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane.
- Such crosslinking agents in amounts between 0 and 2, preferably between 0 and 1 wt.% Contained in the compositions.
- the zinc compounds acting as accelerators it is possible to choose between the zinc salts of fatty acids, zinc dithiocarbamates, basic zinc carbonates and, in particular, finely divided zinc oxide.
- the content of zinc compounds is in the range between 0.5 and 10 wt.%, Preferably between 2 and 8 wt.%.
- other typical rubber vulcanization aids such as fatty acids (e.g., stearic acid) may be present in the formulation.
- a combined vulcanization system of elemental sulfur, the abovementioned organic accelerators and quinone dioximes can also be used.
- p-benzoquinone dioxime may be mentioned.
- other quinone dioximes may also be used in combination with the aforementioned sulfur systems.
- the vulcanization system can only consist of quinone dioximes.
- compositions of the invention for rubber mixtures conventional fillers, accelerators, crosslinking agents such as sulfur and / or peroxides, antioxidants, co-activators and other catalysts, carbon blacks, blowing agents, oils, anti-aging agents, fibers may also include graphite, rheology aids, adhesion promoters, pigments and thermoplastic Contain polymers.
- compositions of the invention may further contain finely divided thermoplastic polymer powders. These should have a glass transition temperature in the range between -80 ° C and 50 ° C.
- suitable thermoplastic polymers are polypropylene, polyethylene, thermoplastic polyurethanes, (meth) acrylate copolymers, styrene copolymers, polyvinyl chloride, polyvinyl acetal and polyvinyl acetate and its copolymers, especially ethylene vinyl acetate (EVA).
- EVA ethylene vinyl acetate
- the mean particle size should be less than 1 mm, preferably less than 350 ⁇ m, more preferably between 100 and 20 ⁇ m. If thermoplastic polymer powders are used, their proportion of the total formulation is between 1 and 20% by weight, preferably between 5 and 15% by weight.
- the fillers may be selected from a variety of materials, particularly chalks, natural or ground calcium carbonates, calcium magnesium carbonates, silicates, talc, barite and carbon black. It may be expedient if at least some of the fillers are surface-pretreated. In particular, a coating with stearic acid has proven to be useful for reducing the moisture introduced and for reducing the moisture sensitivity of the cured composition in the various calcium carbonates or chalks.
- the compositions according to the invention may also contain between 0 and 8% by weight, preferably between 1 and 6% by weight, of calcium oxide.
- the total content of fillers in the formulation can vary between 10 and 80 wt.%, The preferred range is between 20 and 65 wt.%.
- stabilizers or anti-aging agents such as sterically hindered phenols (for example 2,2-methylenebis (4-methyl-6-tert-butylphenol)) or amine derivatives, can be used against the thermal, thermooxidative or ozone degradation of the compositions according to the invention Typical ranges of amounts for these stabilizers are 0 to 2% by weight.
- rheology of the compositions of the present invention can also be brought within the desired range by the selection of fillers and the ratio of low molecular weight liquid rubbers, conventional rheology aids, e.g. fumed silicas, bentones or fibrillated or pulp short fibers in the range between 0.1 and 7% or hydrogenated castor oil derivatives - known e.g. under the trade name Rilanit (Cognis) - be added.
- Rilanit e.g. under the trade name Rilanit (Cognis)
- other conventional auxiliaries and additives can be used in the compositions of the invention.
- blowing agents can be used to achieve the foaming during the curing process, but preferably organic blowing agents from the class of azo compounds, N-nitroso compounds, sulfonyl hydrazides or sulfonyl semicarbazides.
- the azobisisobutyronitrile and in particular the azodicarbonamide are mentioned by way of example ; from the class of the nitroso compounds the di-nitrosopentamethylenetetramine is mentioned by way of example, from the class of the sulfohydrazides the 4,4'-oxybis (benzenesulfonic acid) hydrazide, the diphenylsulfone-3 , 3'-disulfohydrazide or the benzene-1,3-disulfohydrazide and from the class of semicarbazides called p-Toluolsulfonylsemicarbazid.
- expandable microspheres ie non-expanded thermoplastic polymer powders impregnated or filled with low-boiling organic liquids
- Such "Microspheres” are for example in the EP-A-559254 , of the EP-A-586 541 or the EP-A-594 598 described.
- already expanded hollow microspheres can be used or used.
- these expandable / expanded hollow microspheres can be combined in any proportion with the above-mentioned "chemical" blowing agents.
- the chemical blowing agents are used in foamable compositions Amounts between 0.1 and 3 wt.%, Preferably between 0.2 and 2 wt.%,
- the hollow microspheres between 0.1 and 4 wt.%, Preferably between 0.2 and 2 wt.% Used.
- compositions according to the invention generally already have very good adhesion to the substrates owing to the preferred content of liquid rubber having functional groups, if necessary tackifiers and / or adhesion promoters can be added.
- tackifiers and / or adhesion promoters can be added.
- hydrocarbon resins, phenolic resins, terpene-phenolic resins, resorcinol resins or their derivatives, modified or unmodified resin acids or esters (abietic acid derivatives), polyamines, polyaminoamides, anhydrides and anhydride-containing copolymers are suitable.
- the addition of polyepoxide resins in small amounts may improve the adhesion of some substrates.
- the solid epoxy resins having a molecular weight of more than 700 in finely ground form are preferably used.
- tackifiers their nature and amount depends on the polymer composition as well as the substrate to which the composition is applied.
- Typical tackifying resins (tackifiers) such as e.g. Terpene-phenolic resins or resin acid derivatives are used in concentrations between 5 and 20% by weight, typical adhesion promoters such as polyamines, polyaminoamides or phenolic resins or resorcinol derivatives are used in the range between 0.1 and 10% by weight.
- the compositions of the invention are free of plasticizers and extender oils.
- extender oils ie aliphatic, aromatic or naphthenic oils.
- extender oils amounts are used in the range between 2 and 15 wt.%.
- compositions according to the invention preferably contain (stated in% by weight): general composition preferred composition particularly preferred composition hard rubber 0-15% 0-12% 0-9.0%
- Polybutadiene liquid (MW 5000), (10-20% vinyl 1,2-, 50-60% trans 1,4-, 25-35% cis 1,4) 2-50% 5-42% 8-36%
- fillers such as graphite, fibers, talc, silicates, clays, other typical accelerators, crosslinking agents such as peroxides, other antioxidants, co-activators and other catalysts, propellants, oils, anti-aging agents can be used.
- rheology aids, adhesion promoters, pigments and thermoplastic polymers may also be included in the composition. The sum of the constituents of the composition is in every case 100% complete.
- the hot-curing, reactive, one-component adhesives according to the invention can, like the hitherto known rubber-based adhesives, be shell-shaped be used, for example, for Bördelnahtverklebitch or overlapping bonds. They can be applied to oiled sheets, such as those used in automotive bodywork, and the components are then joined.
- the compositions according to the invention do not require any precuring mechanisms such as induction heating, shell furnaces or IR radiators for precuring since, like the rubber compositions known hitherto, they are resistant to washing. Compared to the previously known rubber compositions, they have a much higher elasticity and are able to absorb high energy in the form of percussion work or percussion energy in the adhesive joint.
- the rubber compositions according to the invention have very good impact peel properties in the cured state. These properties are desirable so that the structurally bonded components meet the modern safety requirements (crash behavior) in vehicle construction even in the event of an accident. Because the compositions according to the invention can be formulated without expensive special polymers or copolymers, they can be produced particularly inexpensively.
- compositions according to the invention can be prepared in a manner known per se in high-shear mixing units, including e.g. Kneader, planetary mixer, internal mixer, so-called “Banbury mixer” and similar mixing units known in the art.
- high-shear mixing units including e.g. Kneader, planetary mixer, internal mixer, so-called “Banbury mixer” and similar mixing units known in the art.
- the adhesive compositions listed below were prepared by mixing the components to an evacuable laboratory kneader.
- precipitated calcium carbonate 20.00 low molecular weight polybutadiene oil (MW 1800), vinyl 50% 19.00 low molecular weight stereospecific polybutadiene oil 2) 7.55 sulfur 6.50 ZMBT 2.50
- Polybutadiene with active carboxyl groups (MW 2100) 10.00 Calcium carbonate, coated with stearate 15.00 MBTS 0.95 Disodium salt of hexamethylene-1,6-bis (thiosulfate) 0.50 Hollow microspheres 0.20 Polyvinyl acetate, EVA copolymer, T g about 40 ° C. 8.50
- test specimens made of sheet steel for the determination of the tensile shear strength - dimensions of the adhesive joint 25x12.5x0.2 mm - and the impact peel energy were prepared.
- the test specimens cured to cure the Ktebstoffmischung for 30 minutes at 180 ° C in a convection oven.
- the adhesive compositions based on liquid rubbers according to the prior art provide both higher tensile shear strengths and significantly higher impact peel strength compared to comparable rubber compositions, especially at room temperature but also at low temperatures up to -30 ° C.
- This higher impact peeling is an essential criterion for vehicle construction, since such bonds can absorb much more energy in the event of a shock load in accidents.
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Abstract
Description
Die vorliegende Erfindung betrifft eine einkomponentige, heißhärtende reaktive Zusammensetzung auf der Basis von natürlichen und/oder synthetischen olefinische Doppelbindungen enthaltenden Elastomeren und Vulkanisationsmitteln sowie deren Verwendung als einkomponentiger Klebstoff, Dichtstoff, Versiegelungsmasse oder Beschichtungsmasse im Fahrzeugbau, insbesondere im Automobilrohbau.The present invention relates to a one-component, hot-curing reactive composition based on natural and / or synthetic olefinic double bonds containing elastomers and vulcanizing agents and their use as one-component adhesive, sealant, sealant or coating composition in vehicle construction, especially in automotive body.
Im Maschinen-, Fahrzeug- oder Gerätebau, insbesondere im Flugzeugbau, Schienenfahrzeugbau oder Kraftfahrzeugbau werden die Bauteile aus den verschiedenen metallischen Komponenten und/oder Verbundwerkstoffen in zunehmendem Maße mit Hilfe von Klebstoffen gefügt. Für strukturelle Klebungen werden dabei hohe Anforderungen an die Festigkeit des Klebeverbundes gestellt. Hochfeste und gleichzeitig schlagzähe, schälfeste und schlagschälfeste Klebstoffe, die heute für die Anwendung im Automobilrohbau eingesetzt werden, sind bisher hauptsächlich auf Basis von Epoxiden und Elastomer-modifizierten Epoxiden bzw. Acrylaten bekannt.In machine, vehicle or equipment construction, in particular in aircraft construction, rail vehicle construction or motor vehicle construction, the components made of the various metallic components and / or composite materials are increasingly joined with the aid of adhesives. For structural bonds high demands are placed on the strength of the adhesive bond. High-strength and impact-resistant, peel-resistant and impact peel-resistant adhesives, which are used today for use in automobile body construction, have hitherto been known mainly on the basis of epoxides and elastomer-modified epoxides or acrylates.
Dabei werden diese heißhärtenden, reaktiven Klebstoffe (oft auch als Heißschmelzklebstoffe formuliert) für Bördeinahtverklebungen bzw. überlappende Klebungen im Rohbau auf beöltes Blech aufgetragen und gefügt. Die Aushärtung der hierbei eingesetzten Klebstoffe oder Dichtstoffe erfolgt später in den Lacktrockenöfen. Vorher durchlaufen die geklebten bzw. abgedichteten oder versiegelten Teile Reinigungs-, Phosphatier- und Tauchgrundierungsstufen. Durch die in diesen Stufen verwendeten Behandlungsmittel können die Kleb- bzw. Dicht- oder Versiegelungsmittel aus den Klebefugen gespült werden. Um dieses zu verhindern, wird das Kleb-, Dicht- oder Versiegelungsmittel mittels Vorhärtungsmechanismen wie zum Beispiel mit Induktionsheizungen, Rohbauöfen, Infrarot-Strahlern vorgehärtet oder rheologisch entsprechend eingestellt, um die nachfolgende Vorbehandlung zu überstehen ohne ausgewaschen zu werden. Zusätzlich können Schweißpunkte zur Versteifung der Karosserieteile gesetzt werden. Die Aushärtung der Klebstoffe erfolgt beim Durchlaufen der anschließenden Lacköfen (für den Kathodischen Tauchlack (KTL), Füller, Decklack, etc.).These hot-curing, reactive adhesives (often formulated as hot melt adhesives) for Bördeinahtverklebungen or overlapping bonds in the shell on oiled sheet applied and joined. The curing of the adhesives or sealants used in this case takes place later in the paint drying ovens. Previously, the bonded or sealed or sealed parts undergo cleaning, phosphating and dipping priming steps. The treatment agents used in these stages can be used to rinse the adhesives or sealants from the adhesive joints. To prevent this, the adhesive, sealant or sealant is used by means of precuring mechanisms, such as induction heating, Shell furnaces, pre-hardened or rheologically adjusted infrared emitters to survive the subsequent pretreatment without being washed out. In addition, welding points can be used to reinforce the body parts. The curing of the adhesives takes place when passing through the subsequent paint ovens (for the cathodic dip paint (KTL), filler, topcoat, etc.).
Aus der
Die
Die
In ähnlicher Weise beschreibt
Hierin soll R Wasserstoff oder eine Methylgruppe sein, R' ist Wasserstoff oder C1 bis C3-Alkyl, insbesondere Wasserstoff oder Ethyl und R" soll eine C3-C20-Alkylgruppe oder eine Phenoxygruppe oder eine Alkoxygruppe sein. Als weitere Komponente soll ein Elastomer mit einem Molekulargewichtbereich zwischen 1000 und 9000 mit (meth)acrylatischen Gruppen in der Zusammensetzung anwesend sein. Diese Schrift gibt an, dass die dort offenbarten Zusammensetzungen besonders zum Kleben von Materialien mit unterschiedlichen thermischen Expansions-Koeffizienten geeignet sind, wie sie zum Beispiel in der Fahrzeugindustrie Einsatz finden. Exemplarisch genannt ist die Klebung von Seitenblechen von Trailern oder die Direktverglasung. Es wird angegeben, dass diese Zusammensetzungen eine sehr hohe Schlagfestigkeit bei tiefen Temperaturen aufweisen.Here, R is hydrogen or a methyl group, R 'is hydrogen or C 1 to C 3 -alkyl, in particular hydrogen or ethyl and R "is a C 3 -C 20 -alkyl group or a phenoxy group or an alkoxy group an elastomer having a molecular weight range between 1000 and 9000 with (meth) acrylate groups in the composition is present This document indicates that the compositions disclosed therein are particularly suitable for bonding materials having different thermal expansion coefficients, as described, for example, in US Pat The adhesion of side panels of trailers or direct glazing is mentioned by way of example: it is stated that these compositions have a very high impact strength at low temperatures.
Nachteile der vorgenannten Klebstoffe auf Epoxid- oder (Meth)acrylat-Basis sind:
- hohe Rohstoffkosten,
- die notwendige arbeitshygienische Kennzeichnung (meistens mit Xi),
- bedingte Ölaufnahme,
- mangelnder Korrosionsschutz,
- mangelnde Alterungsbeständigkeit.
- high raw material costs,
- the necessary occupational hygiene labeling (mostly with Xi),
- conditional oil intake,
- lack of corrosion protection,
- lack of aging resistance.
Es sind auch hochfeste Klebstoffe auf Kautschukbasis bekannt geworden. Die
Aus der
Aus der
From the
Die hochfesten Klebstoffe des vorgenannten Standes der Technik auf Kautschukbasis sind in Ihren Eigenschaften bei tiefen Temperaturen verbesserungsbedürftig, sie weisen insbesondere bei tiefen Temperaturen keine elastischen und schlagzähen Eigenschaften auf, da sie, vermutlich aufgrund des hohen Vernetzungsgrades, bei tiefen Temperaturen zu stark verspröden.The high-strength adhesives of the abovementioned state of the art based on rubber require improvement in their properties at low temperatures; they have no elastic and impact-resistant properties, especially at low temperatures, since they embrittle too much at low temperatures, presumably because of the high degree of crosslinking.
Aufgabe der vorliegenden Erfindung war daher, hochfeste und gleichzeitig schlagzähe Klebstoffe bereitzustellen, die für die Anwendung im Automobilrohbau eingesetzt werden können und die nicht Epoxidharze oder (Meth)acrylatharze als wesentlichen Bestandteil enthalten, ohne die Verwendung teurer Spezialpolymerer oder Copolymerer.The object of the present invention was therefore to provide high-strength and impact-resistant adhesives which can be used for automotive OEM applications and which do not contain epoxy resins or (meth) acrylate resins as an essential component without the use of expensive specialty polymers or copolymers.
Die erfindungsgemäße Lösung der Aufgabe ist den Patentansprüchen zu entnehmen, sie besteht im Wesentlichen in der Bereitstellung einer einkomponentigen, heißhärtenden reaktiven Zusammensetzung auf der Basis von natürlichen und/oder synthetischen olefinische Doppelbindungen enthaltenden Elastomeren und Vulkanisationsmitteln, die
- a) mindestens ein flüssiges Polyen mit einem Molekulargewicht zwischen 400 und 80.000, vorzugsweise zwischen 800 und 25.000,
- b) mindesten ein flüssiges Polybutadien mit 10 - 20 % vinyl 1,2-, 50 - 60 % trans 1,4-, 25 - 35 % cis 1,4- Doppelbindungen als Mikrostruktur und
- c) ein Vulkanisationssystem aus Schwefel und Beschleunigern undloder ggf. Chinonoximen enthält.
- a) at least one liquid polyene having a molecular weight between 400 and 80,000, preferably between 800 and 25,000,
- b) at least one liquid polybutadiene with 10 - 20% vinyl 1,2-, 50- 60% trans 1,4-, 25- 35% cis 1,4 double bonds as a microstructure and
- c) contains a vulcanization system of sulfur and accelerators andlor possibly quinone oximes.
Unter "flüssig" wird hier "flüssig bei Raumtemperatur (22°C)" verstanden.By "liquid" is meant "liquid at room temperature (22 ° C)".
Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung der vorgenannten heißhärtenden, reaktiven Zusammensetzungen als einkomponentiger Klebstoff, Dichtstoff oder Beschichtungsmasse oder Versiegelungsmasse im Automobilrohbau.Another object of the present invention is the use of the above-mentioned hot-curing, reactive compositions as a one-component adhesive, sealant or coating composition or sealant in automotive body.
Das oder die flüssigen Polyen(e) oder Elastomere a) enthalten dabei pro Molekül mindestens eine olefinisch ungesättigte Doppelbindung. Sie können dabei aus der folgenden Gruppe der Homo- und/oder Copolymeren ausgewählt werden:The liquid polyene (s) or elastomers a) contain at least one olefinically unsaturated double bond per molecule. They can be selected from the following group of homopolymers and / or copolymers:
Polybutadiene, insbesondere die 1,3- und 1,2-Poly-butadiene, Polybutene, Polyisobutylene, 1,4- und 3,4-Polyisoprene, Styrol-Butadien-Copolymere. Butadien-Acrylnitril-Copolymere, wobei eines oder mehrere dieser Polymeren endständige und/oder (statistisch verteilte) seitenständige funktionelle Gruppen haben können. Beispiele für derartige funktionelle Gruppen sind Hydroxy-, Amino-, Carboxyl-, Carbonsäureanhydrid- oder Epoxygruppen. Das Molekulargewicht dieser Flüssigkautschuke ist typischerweise unterhalb von 80 000 und oberhalb von 400, vorzugsweise zwischen 800 und 25 000. Der Anteil an Flüssigkautschuk an der Gesamtzusammensetzung hängt dabei von der gewünschten Rheologie der ungehärteten Zusammensetzung und der erwünschten mechanischen Steifigkeit oder Festigkeit des Verbundes und gegebenenfalls den akustischen Dämpfungseigenschaften der ausgehärteten Zusammensetzung ab. Der Anteil an flüssigem Kautschuk bzw. Elastomer variiert normalerweise zwischen 2 und 55 Gew.% der Gesamtformulierung. Dabei hat es sich als zweckmäßig erwiesen, vorzugsweise Mischungen von Flüssigkautschuken unterschiedlicher Molekulargewichte und unterschiedlicher Konfiguration in Bezug auf die restlichen Doppelbindungen einzusetzen. Außerdem können als Copolymere sowohl Blockcopolymere als auch solche mit statistischer Verteilung der Comonomeren eingesetzt werden. Zur Erzielung optimaler Haftung auf den diversen Substraten wird in den besonders bevorzugten Formulierungen anteilig eine Flüssigkautschukkomponente mit Hydroxylgruppen, Carboxylgruppen bzw. Säureanhydridgruppen eingesetzt. Der Anteil an carboxylgruppenhaltigem Flüssigkautschuk kann 0 bis 25 Gew.%, vorzugsweise 1 bis 15 und ganz besonders bevorzugt 3 bis 10 Gew.% betragen.Polybutadienes, in particular the 1,3- and 1,2-poly-butadienes, polybutenes, polyisobutylenes, 1,4- and 3,4-polyisoprenes, styrene-butadiene copolymers. Butadiene-acrylonitrile copolymers, wherein one or more of these polymers may have terminal and / or (randomly distributed) pendant functional groups. Examples of such functional groups are hydroxy, amino, carboxyl, carboxylic anhydride or epoxy groups. The molecular weight of these liquid rubbers is typically below 80,000 and above 400, preferably between 800 and 25,000. The proportion of liquid rubber in the overall composition depends on the desired rheology of the uncured composition and the desired mechanical stiffness or strength of the composite and, if applicable acoustic damping properties of the cured composition from. The proportion of liquid rubber or elastomer normally varies between 2 and 55% by weight of the total formulation. It has proven to be expedient, preferably mixtures of liquid rubbers of different Molecular weights and different configuration with respect to the remaining double bonds. In addition, both block copolymers and those with random distribution of the comonomers can be used as copolymers. To achieve optimum adhesion to the various substrates, a liquid rubber component having hydroxyl groups, carboxyl groups or acid anhydride groups is proportionately used in the particularly preferred formulations. The proportion of carboxyl group-containing liquid rubber may be from 0 to 25% by weight, preferably from 1 to 15 and very particularly preferably from 3 to 10% by weight.
Ein wesentlicher Bestandteil der erfindungsgemäßen Zusammensetzungen sind flüssige Polybutadiene, vorzugsweise mit enger Molekulargewichtsverteilung, die durch anionische Polymerisation herstellbar sind. Diese niedermolekularen flüssigen Polybutadiene enthalten in der Polymerkette drei Strukturtypen: vinylische 1,2-Doppelbindungen, cis 1,4-Doppelbindungen und trans 1,4-Doppelbindungen, wobei diese flüssigen Polymeren 10 bis 20 % vinylische 1,2-Doppelbindungen, 50 bis 60 % trans 1,4-Doppelbindungen und 25 bis 35 % cis 1,4-Doppelbindungen in ihrer Mikrostruktur aufweisen. Die Molekulargewichte dieser flüssigen Butadiene liegen zwischen 2.000 und 12.000, vorzugsweise zwischen 5.000 und 9.000 (zahlenmittleres Molekulargewicht). Aufgrund ihrer engen Molekulargewichtsverteilung weisen sie eine sehr niedrige Viskosität zwischen 3 und 15 Pa·s bei 25°C auf. Sie können gegebenenfalls, bedingt durch die anionische Polymerisation, eine oder zwei terminale bzw. eine oder mehrere statistisch verteilte Hydroxylgruppe(n) pro Molekül aufweisen. Alternativ können diese Polymere auch eine oder zwei terminale bzw. eine oder mehrere statistisch verteilte Carboxylgruppe(n) aufweisen. Der Vorteil des Einsatzes dieser flüssigen Polybutadiene mit enger Molekulargewichtsverteilung ist ein höheres Molekulargewicht im Vergleich zu üblichen flüssigen Polybutadienen bei trotzdem niedriger Viskosität.An essential constituent of the compositions according to the invention are liquid polybutadienes, preferably having a narrow molecular weight distribution, which can be prepared by anionic polymerization. These low molecular weight liquid polybutadienes contain three structural types in the polymer chain: vinylic 1,2-double bonds, cis 1,4-double bonds and trans 1,4-double bonds, these liquid polymers having 10 to 20% vinylic 1,2-double bonds, 50 to 60 have% trans 1,4 double bonds and 25 to 35% cis 1,4 double bonds in their microstructure. The molecular weights of these liquid butadienes are between 2,000 and 12,000, preferably between 5,000 and 9,000 (number average molecular weight). Due to their narrow molecular weight distribution they have a very low viscosity between 3 and 15 Pa · s at 25 ° C. Depending on the anionic polymerization, they may optionally have one or two terminal or one or more randomly distributed hydroxyl group (s) per molecule. Alternatively, these polymers may also have one or two terminal or one or more randomly distributed carboxyl group (s). The advantage of using these narrow molecular weight distribution liquid polybutadienes is a higher molecular weight compared to conventional liquid polybutadienes with nevertheless low viscosity.
Zusätzlich kann die erfindungsgemäße Klebstoff-Zusammensetzung auch noch einen Anteil an Festkautschuken enthalten. Geeignete Festkautschuke haben im Vergleich zu den Flüssigkautschuken ein signifikant höheres Molekulargewicht (MW=100000 oder höher). Beispiele für geeignete Kautschuke sind Polybutadien, vorzugsweise mit einem sehr hohen Anteil an cis-1,4-Doppelbindungen (typischerweise über 95%), Styrol-Butadien-Kautschuk, Butadien-Acrylnitril-Kautschuk, synthetischer oder natürlicher Isoprenkautschuk, Polycyclooctenamer, Butylkautschuk oder Polyurethankautschuk. Der Anteil an Festkautschuk kann dabei bis zu 15 Gew.% betragen, vorzugsweise liegt er zwischen 0 und 12 Gew.% und ganz besonders bevorzugt zwischen 0 und 9 Gew.%.In addition, the adhesive composition of the invention may also contain a proportion of solid rubbers. Suitable solid rubbers have in Compared to the liquid rubbers, a significantly higher molecular weight (MW = 100,000 or higher). Examples of suitable rubbers are polybutadiene, preferably with a very high proportion of cis-1,4-double bonds (typically over 95%), styrene-butadiene rubber, butadiene-acrylonitrile rubber, synthetic or natural isoprene rubber, polycyclooctenamer, butyl rubber or polyurethane rubber , The proportion of solid rubber may be up to 15% by weight, preferably between 0 and 12% by weight and very particularly preferably between 0 and 9% by weight.
Weiterhin enthalten die erfindungsgemäßen einkomponentigen, heißhärtenden reaktiven Zusammensetzungen ein Vulkanisationssystem aus Schwefel und Beschleunigern und/oder ggf. Chinonoximen.Furthermore, the one-component, hot-curing reactive compositions according to the invention comprise a vulcanization system of sulfur and accelerators and / or optionally quinone oximes.
Für das Vulkanisationssystem eignen sich eine Vielzahl von Vulkanisationsmitteln in Kombination mit elementarem Schwefel, aber auch Vulkanisationssysteme ohne freien Schwefel. Zu letzteren zählen die Vulkanisationssysteme auf der Basis von Thiuramdisulfiden, organischen Peroxiden, polyfunktionellen Aminen, Chinonen, p-Benzochinondioxim, p-Nitrosobenzol und Dinitrosobenzol oder auch die Vernetzung mit (blockierten) Diisocyanaten. Ganz besonders bevorzugt sind jedoch Vulkanisationssysteme auf der Basis von elementarem Schwefel und organischen Vulkanisationsbeschleunigern sowie Zinkverbindungen. Der pulverförmige Schwefel wird dabei in Mengen von 4 bis 25 Gew.%, bezogen auf die Gesamtzusammensetzung eingesetzt, besonders bevorzugt werden Mengen zwischen 5 und 15 Gew.% eingesetzt. Als organische Beschleuniger eignen sich Dithiocarbamate (in Form ihrer Ammonium- bzw. Metallsalze), Xanthogenate, Thiuram-Verbindungen (Monosulfide und Disulfide), Thiazolverbindungen, Aldehyd/Aminbeschleuniger (z.B. Hexamethylentetramin) sowie Guanidinbeschleuniger, ganz besonders bevorzugt wird Dibenzothiazyldisulfid (MBTS), 2-Mercaptobenzthiazol (MBT), dessen Zinksalz (ZMBT), Zinkdibenzyldithiocarbamat (ZBEC), N-Cyclohexylbenzodithiazylsulfenamid (CBS) oder Diphenylguanidin. Die Beschleuniger werden in Mengen zwischen 0,25 und 8,0 Gew.%, besonders bevorzugt zwischen 0,4 und 6 Gew.%, verwendet. Für die Erzielung besonders hoher Temperatur- und Reversionsfestigkeit des Klebstoffes kann das Vulkanisationsgemisch auch bifunktionelle Vernetzer enthalten. Konkrete Beispiele sind Vernetzer auf Basis von bifunktionellen Dithiocarbamaten wie z.B. das 1,6-bis(N,N-dibenzylthiocarbamoyldithio)-hexan. Derartige Vernetzer in Mengen zwischen 0 und 2, vorzugsweise zwischen 0 und 1 Gew.% in den Zusammensetzungen enthalten.For the vulcanization system, a variety of vulcanizing agents are suitable in combination with elemental sulfur, but also vulcanization systems without free sulfur. The latter include the vulcanization systems based on thiuram disulfides, organic peroxides, polyfunctional amines, quinones, p-benzoquinone dioxime, p-nitrosobenzene and dinitrosobenzene, or crosslinking with (blocked) diisocyanates. However, very particular preference is given to vulcanization systems based on elemental sulfur and organic vulcanization accelerators and zinc compounds. The powdered sulfur is used in amounts of 4 to 25 wt.%, Based on the total composition, more preferably amounts are used between 5 and 15 wt.%. Suitable organic accelerators are dithiocarbamates (in the form of their ammonium or metal salts), xanthates, thiuram compounds (monosulfides and disulfides), thiazole compounds, aldehyde / amine accelerators (eg hexamethylenetetramine) and guanidine accelerators, very particular preference is given to dibenzothiazyl disulfide (MBTS), 2 Mercaptobenzothiazole (MBT), its zinc salt (ZMBT), zinc dibenzyldithiocarbamate (ZBEC), N-cyclohexylbenzodithiazyl sulfenamide (CBS) or diphenylguanidine. The accelerators are used in amounts between 0.25 and 8.0 wt.%, Particularly preferably between 0.4 and 6 wt.%. For the achievement especially high temperature and reversion of the adhesive, the vulcanization mixture may also contain bifunctional crosslinkers. Specific examples are crosslinkers based on bifunctional dithiocarbamates such as 1,6-bis (N, N-dibenzylthiocarbamoyldithio) hexane. Such crosslinking agents in amounts between 0 and 2, preferably between 0 and 1 wt.% Contained in the compositions.
Bei den als Beschleuniger wirkenden Zinkverbindungen kann zwischen den Zinksalzen von Fettsäuren, Zinkdithiocarbamaten, basischen Zinkcarbonaten sowie insbesondere feinteiligem Zinkoxid gewählt werden. Der Gehalt an Zinkverbindungen liegt im Bereich zwischen 0,5 und 10 Gew.%, vorzugsweise zwischen 2 und 8 Gew.%. Zusätzlich können weitere typische Kautschuk-Vulkanisationshilfsmittel wie Fettsäuren (z.B. Stearinsäure) in der Formulierung vorhanden sein.In the case of the zinc compounds acting as accelerators, it is possible to choose between the zinc salts of fatty acids, zinc dithiocarbamates, basic zinc carbonates and, in particular, finely divided zinc oxide. The content of zinc compounds is in the range between 0.5 and 10 wt.%, Preferably between 2 and 8 wt.%. In addition, other typical rubber vulcanization aids such as fatty acids (e.g., stearic acid) may be present in the formulation.
Erfingdungsgemäß kann auch ein kombiniertes Vulkanisationssystem aus elementarem Schwefel, den oben genannten organischen Beschleunigern und Chinondioximen eingesetzt werden. Beispielhaft erwähnt sei p-Benzochinondioxim. Es können jedoch auch andere Chinondioxime in Kombination mit den vorgenannten Schwefelsystemen verwendet werden. Das Vulkanisationssystem kann auch nur aus Chinondioximen bestehen.According to the invention, a combined vulcanization system of elemental sulfur, the abovementioned organic accelerators and quinone dioximes can also be used. As an example, p-benzoquinone dioxime may be mentioned. However, other quinone dioximes may also be used in combination with the aforementioned sulfur systems. The vulcanization system can only consist of quinone dioximes.
Zusätzlich können die erfindungsgemäßen Zusammensetzungen für Kautschukmischungen übliche Füllstoffe, Beschleuniger, Vernetzungsmittel wie Schwefel und/oder Peroxide, Antioxidantien, Co-Aktivatoren und weitere Katalysatoren, Ruße, Treibmittel, Öle, Alterungsschutzmittel, Fasern ggf. auch Graphit, Rheologiehilfsmittel, Haftungsvermittler, Pigmente und thermoplastische Polymere enthalten.In addition, the compositions of the invention for rubber mixtures conventional fillers, accelerators, crosslinking agents such as sulfur and / or peroxides, antioxidants, co-activators and other catalysts, carbon blacks, blowing agents, oils, anti-aging agents, fibers may also include graphite, rheology aids, adhesion promoters, pigments and thermoplastic Contain polymers.
Die erfindungsgemäßen Zusammensetzungen können weiterhin feinverteilte thermoplastischen Polymerpulver enthalten. Diese sollten eine Glasübergangstemperatur im Bereich zwischen -80°C und 50°C aufweisen. Beispiele für geeignete thermoplastische Polymere sind Polypropylen, Polyethylen, thermoplastische Polyurethane, (Meth)acrylatcopolymere, Styrolcopolymere, Polyvinylchlorid, Polyvinylacetal sowie Polyvinylacetat und dessen Copolymere, insbesondere Ethylenvinylacetat (EVA). Obwohl die Teilchengröße bzw. Teilchengrößenverteilung des thermoplastischen Polymerpulvers nicht besonders kritisch ist, sollte die mittlere Teilchengröße unter 1 mm, vorzugsweise unter 350 µm, besonders bevorzugt zwischen 100 und 20 µm liegen. Wenn thermoplastische Polymerpulver mitverwendet werden, liegt ihr Anteil an der Gesamtformulierung zwischen 1 und 20 Gew.%, vorzugsweise zwischen 5 und 15 Gew.%.The compositions of the invention may further contain finely divided thermoplastic polymer powders. These should have a glass transition temperature in the range between -80 ° C and 50 ° C. examples for suitable thermoplastic polymers are polypropylene, polyethylene, thermoplastic polyurethanes, (meth) acrylate copolymers, styrene copolymers, polyvinyl chloride, polyvinyl acetal and polyvinyl acetate and its copolymers, especially ethylene vinyl acetate (EVA). Although the particle size or particle size distribution of the thermoplastic polymer powder is not particularly critical, the mean particle size should be less than 1 mm, preferably less than 350 μm, more preferably between 100 and 20 μm. If thermoplastic polymer powders are used, their proportion of the total formulation is between 1 and 20% by weight, preferably between 5 and 15% by weight.
Die Füllstoffe können aus einer Vielzahl von Materialien ausgewählt werden, insbesondere sind hier zu nennen Kreiden, natürliche oder gemahlene Calciumcarbonate, Calcium-Magnesiumcarbonate, Silikate, Talkum, Schwerspat sowie Ruß. Es kann ggf. zweckmäßig sein, dass zumindest ein Teil der Füllstoffe oberflächenvorbehandelt ist, insbesondere hat sich bei den verschiedenen Calciumcarbonaten bzw. Kreiden eine Beschichtung mit Stearinsäure zur Verminderung der eingetragenen Feuchtigkeit und zur Verminderung der Feuchtigkeitsempfindlichkeit der ausgehärteten Zusammensetzung als zweckmäßig erwiesen. Die erfindungsgemäßen Zusammensetzungen können noch zwischen 0 und 8 Gew.%, vorzugsweise zwischen 1 und 6 Gew.% an Calciumoxid enthalten. Der Gesamtanteil an Füllstoffen in der Formulierung kann zwischen 10 und 80 Gew.% variieren, der Vorzugsbereich liegt zwischen 20 und 65 Gew.%.The fillers may be selected from a variety of materials, particularly chalks, natural or ground calcium carbonates, calcium magnesium carbonates, silicates, talc, barite and carbon black. It may be expedient if at least some of the fillers are surface-pretreated. In particular, a coating with stearic acid has proven to be useful for reducing the moisture introduced and for reducing the moisture sensitivity of the cured composition in the various calcium carbonates or chalks. The compositions according to the invention may also contain between 0 and 8% by weight, preferably between 1 and 6% by weight, of calcium oxide. The total content of fillers in the formulation can vary between 10 and 80 wt.%, The preferred range is between 20 and 65 wt.%.
Gegen den thermischen, thermooxidativen oder Ozon - Abbau der erfindungsgemäßen Zusammensetzungen können konventionelle Stabilisatoren oder Alterungsschutzmittel, wie z.B. sterisch gehinderte Phenole (beispielsweise 2,2-Methylen-bis-(4-methyl-6-tert.-butylphenol)) oder Aminderivate eingesetzt werden, typische Mengenbereiche für diese Stabilisatoren sind 0 bis 2 Gew.%.Conventional stabilizers or anti-aging agents, such as sterically hindered phenols (for example 2,2-methylenebis (4-methyl-6-tert-butylphenol)) or amine derivatives, can be used against the thermal, thermooxidative or ozone degradation of the compositions according to the invention Typical ranges of amounts for these stabilizers are 0 to 2% by weight.
Obwohl die Rheologie der erfindungsgemäßen Zusammensetzungen auch durch die Auswahl der Füllstoffe und das Mengenverhältnis der niedermolekularen Flüssigkautschuke in den gewünschten Bereich gebracht werden kann, können konventionelle Rheologiehilfsmittel wie z.B. pyrogene Kieselsäuren, Bentone oder fibrillierte oder Pulp-Kurzfasern im Bereich zwischen 0,1 und 7% oder auch hydrierte Ricinusöl-Derivate - bekannt z.B. unter dem Handelsnamen Rilanit (Fa. Cognis) - zugesetzt werden. Außerdem können weitere konventionelle Hilfs- und Zusatzmittel in den erfindungsgemäßen Zusammensetzungen Verwendung finden.Although the rheology of the compositions of the present invention can also be brought within the desired range by the selection of fillers and the ratio of low molecular weight liquid rubbers, conventional rheology aids, e.g. fumed silicas, bentones or fibrillated or pulp short fibers in the range between 0.1 and 7% or hydrogenated castor oil derivatives - known e.g. under the trade name Rilanit (Cognis) - be added. In addition, other conventional auxiliaries and additives can be used in the compositions of the invention.
Zum Erzielen der Aufschäumung während des Härtungsvorganges können prinzipiell alle gängigen Treibmittel verwendet werden, vorzugsweise jedoch organische Treibmittel aus der Klasse der Azoverbindungen, N-Nitrosoverbindungen, Sulfonylhydrazide oder Sulfonylsemicarbazide. Für die erfindungsgemäß zu verwendenden Azoverbindungen seien beispielhaft das Azobisisobutyronitril und insbesondere das Azodicarbonamid genannt, aus der Klasse der Nitrosoverbindungen sei beispielhaft das Di-Nitrosopentamethylentetramin genannt, aus der Klasse der Sulfohydrazide das 4,4'-Oxybis-(benzolsulfonsäurehydrazid), das Diphenylsulfon-3,3'-disulfohydrazid oder das Benzol-1,3-disulfohydrazid und aus der Klasse der Semicarbazide das p-Toluolsulfonylsemicarbazid genannt.In principle, all common blowing agents can be used to achieve the foaming during the curing process, but preferably organic blowing agents from the class of azo compounds, N-nitroso compounds, sulfonyl hydrazides or sulfonyl semicarbazides. For the azo compounds to be used according to the invention , the azobisisobutyronitrile and in particular the azodicarbonamide are mentioned by way of example ; from the class of the nitroso compounds the di-nitrosopentamethylenetetramine is mentioned by way of example, from the class of the sulfohydrazides the 4,4'-oxybis (benzenesulfonic acid) hydrazide, the diphenylsulfone-3 , 3'-disulfohydrazide or the benzene-1,3-disulfohydrazide and from the class of semicarbazides called p-Toluolsulfonylsemicarbazid.
An die Stelle der vorgenannten Treibmittel können auch die so genannten expandierbaren Mikrohohlkugeln ("expandable microspheres"), d.h. nicht expandierte thermoplastische Polymerpulver treten, die mit niedrigsiedenden organischen Flüssigkeiten getränkt bzw. gefüllt sind. Derartige "Microspheres" sind beispielsweise in der
Obwohl die erfindungsgemäßen Zusammensetzungen aufgrund des bevorzugten Gehaltes an Flüssigkautschuk mit funktionellen Gruppen in der Regel bereits eine sehr gute Haftung auf den Substraten haben, können, falls erforderlich, Klebrigmacher und/oder Haftvermittler zugesetzt werden. Hierzu eignen sich beispielsweise Kohlenwasserstoffharze, Phenolharze, Terpen-Phenolharze, Resorcinharze oder deren Derivate, modifizierte oder unmodifizierte Harzsäuren bzw. -ester (Abietinsäurederivate), Polyamine, Polyaminoamide, Anhydride und Anhydrid enthaltende Copolymere. Auch der Zusatz von Polyepoxydharzen in geringen Mengen kann bei manchen Substraten die Haftung verbessern. Hierfür werden dann jedoch vorzugsweise die festen Epoxidharze mit einem Molekulargewicht von über 700 in fein gemahlener Form eingesetzt. Falls Klebrigmacher bzw. Haftvermittler eingesetzt werden, hängt deren Art und Menge von der Polymerzusammensetzung sowie dem Substrat, auf welches die Zusammensetzung appliziert wird, ab. Typische klebrigmachende Harze (Tackifier) wie z.B. Terpenphenolharze oder Harzsäurederivate werden in Konzentrationen zwischen 5 und 20 Gew.% verwendet, typische Haftvermittler wie Polyamine, Polyaminoamide oder Phenolharze oder Resorcinderivate werden im Bereich zwischen 0,1 und 10 Gew.% verwendet.Although the compositions according to the invention generally already have very good adhesion to the substrates owing to the preferred content of liquid rubber having functional groups, if necessary tackifiers and / or adhesion promoters can be added. For this purpose, for example, hydrocarbon resins, phenolic resins, terpene-phenolic resins, resorcinol resins or their derivatives, modified or unmodified resin acids or esters (abietic acid derivatives), polyamines, polyaminoamides, anhydrides and anhydride-containing copolymers are suitable. The addition of polyepoxide resins in small amounts may improve the adhesion of some substrates. For this purpose, however, the solid epoxy resins having a molecular weight of more than 700 in finely ground form are preferably used. If tackifiers are used, their nature and amount depends on the polymer composition as well as the substrate to which the composition is applied. Typical tackifying resins (tackifiers) such as e.g. Terpene-phenolic resins or resin acid derivatives are used in concentrations between 5 and 20% by weight, typical adhesion promoters such as polyamines, polyaminoamides or phenolic resins or resorcinol derivatives are used in the range between 0.1 and 10% by weight.
Vorzugsweise sind die erfindungsgemäßen Zusammensetzungen frei von Weichmachern und Extenderölen. Es kann jedoch notwendig sein, die Rheologie der ungehärteten Zusammensetzung und/oder die mechanischen Eigenschaften der gehärteten Zusammensetzung durch Zugabe von sog. Extenderölen, d.h. aliphatischen, aromatischen oder naphtenischen Ölen zu beeinflussen. Vorzugsweise geschieht diese Beeinflussung zwar durch zweckmäßige Auswahl der niedrigmolekularen Flüssigkautschuke oder durch die Mitverwendung von niedermolekularen Polybutenen oder Polyisobutylenen. Falls Extenderöle eingesetzt werden, werden Mengen im Bereich zwischen 2 und 15 Gew.% verwendet.Preferably, the compositions of the invention are free of plasticizers and extender oils. However, it may be necessary to influence the rheology of the uncured composition and / or the mechanical properties of the cured composition by adding so-called extender oils, ie aliphatic, aromatic or naphthenic oils. Although this influence is preferably done by appropriate selection of low molecular weight liquid rubbers or by the concomitant use of low molecular weight polybutenes or polyisobutylenes. If extender oils amounts are used in the range between 2 and 15 wt.%.
Zur Erzielung hochfester, schlagschälfester und schälfester Kautschukmischungen enthalten die erfindungsgemäßen Zusammensetzungen vorzugsweise (Angabe in Gew.%):
Daneben können, wie vorstehend genannt, weitere Füllstoffe wie Graphit, Fasern, Talkum, Silikate, Tonerden, weitere typische Beschleuniger, Vernetzungsmittel wie Peroxide, andere Antioxidantien, Co-Aktivatoren und weitere Katalysatoren, Treibmittel, Öle, Alterungsschutzmittel mit verwendet werden. Ggf. können auch Rheologiehilfsmittel, Haftungsvermittler, Pigmente und thermoplastische Polymere in der Zusammensetzung enthalten sein. Die Summe der Bestandteile der Zusammensetzung ergänzt sich in jedem Falle zu 100 %.In addition, as mentioned above, other fillers such as graphite, fibers, talc, silicates, clays, other typical accelerators, crosslinking agents such as peroxides, other antioxidants, co-activators and other catalysts, propellants, oils, anti-aging agents can be used. Possibly. For example, rheology aids, adhesion promoters, pigments and thermoplastic polymers may also be included in the composition. The sum of the constituents of the composition is in every case 100% complete.
Die erfindungsgemäßen heißhärtenden, reaktiven, einkomponentigen Klebstoffe können wie die bisher bekannten Klebstoffe auf Kautschukbasis im Rohbau eingesetzt werden, beispielsweise für Bördelnahtverklebungen oder überlappende Verklebungen. Sie können auf geölte Bleche, wie sie im Automobilrohbau eingesetzt werden, aufgetragen werden und die Bauteile werden anschließend gefügt. Die erfindungsgemäßen Zusammensetzungen benötigen in der Regel keine Vorhärtungsmechanismen wie Induktionsheizung, Rohbauöfen oder IR-Strahler zur Vorhärtung, da sie wie die bisher bekannten Kautschukzusammensetzungen wäscherbeständig sind. Gegenüber den bisher bekannten Kautschukzusammensetzungen weisen sie eine sehr viel höhere Elastizität auf und sind in der Lage, hohe Energie in Form von Schlagschäl-Arbeit bzw. Schlagschäl-Energie in der Klebstoff-Fuge aufzunehmen. Insbesondere weisen die erfindungsgemäßen Kautschukzusammensetzungen sehr gute Schlagschäl-Eigenschaften im ausgehärteten Zustand auf. Diese Eigenschaften sind erwünscht, damit die strukturell geklebten Bauteile auch im Falle eines Unfalls den modernen Sicherheitsanforderungen (Crash-Verhalten) im Fahrzeugbau entsprechen. Weil die erfindungsgemäßen Zusammensetzungen ohne teure Spezialpolymere oder Copolymere formuliert werden können, lassen sich diese besonders kostengünstig fertigen.The hot-curing, reactive, one-component adhesives according to the invention can, like the hitherto known rubber-based adhesives, be shell-shaped be used, for example, for Bördelnahtverklebungen or overlapping bonds. They can be applied to oiled sheets, such as those used in automotive bodywork, and the components are then joined. As a rule, the compositions according to the invention do not require any precuring mechanisms such as induction heating, shell furnaces or IR radiators for precuring since, like the rubber compositions known hitherto, they are resistant to washing. Compared to the previously known rubber compositions, they have a much higher elasticity and are able to absorb high energy in the form of percussion work or percussion energy in the adhesive joint. In particular, the rubber compositions according to the invention have very good impact peel properties in the cured state. These properties are desirable so that the structurally bonded components meet the modern safety requirements (crash behavior) in vehicle construction even in the event of an accident. Because the compositions according to the invention can be formulated without expensive special polymers or copolymers, they can be produced particularly inexpensively.
Die erfindungsgemäßen Zusammensetzungen können in sich bekannter Weise in Mischaggregaten mit hoher Scherwirkung hergestellt werden, hierzu gehören z.B. Kneter, Planetenmischer, Innenmischer, so genannte "Banbury-Mischer" und ähnliche dem Fachmann bekannte Mischaggregate.The compositions according to the invention can be prepared in a manner known per se in high-shear mixing units, including e.g. Kneader, planetary mixer, internal mixer, so-called "Banbury mixer" and similar mixing units known in the art.
In den nachfolgenden Ausführungsbeispielen soll die Erfindung näher erläutert werden, wobei die Auswahl der Beispiele keine Beschränkung des Umfanges des Erfindungsgegenstandes darstellen soll.In the following embodiments, the invention will be explained in more detail, wherein the selection of examples is not intended to represent a limitation of the scope of the subject invention.
Die nachfolgend aufgeführten Klebstoffzusammensetzungen wurden durch Mischen der Bestandteile einem evakuierbaren Laborkneter hergestellt.The adhesive compositions listed below were prepared by mixing the components to an evacuable laboratory kneader.
- 1) MW = 5000, Mikrostruktur: 10 - 20 % vinyl- 1,2-,50 - 60 % trans 1,4-, 25 - 35 % cis 1,4- Doppelbindungen1) MW = 5000, microstructure: 10-20% vinyl-1,2-, 50-60% trans 1,4-, 25-35% cis 1,4-double bonds
- 2) MW = 1800, vinyl- Doppelbindungen 50 %2) MW = 1800, vinyl double bonds 50%
Mit den vorbeschriebenen Kautschukzusammensetzungen der Beispiele 1 bis 4 wurden Prüfkörper aus Stahlblech für die Bestimmung der Zugscherfestigkeit - Abmessungen der Klebefuge 25x12,5x0,2 mm - sowie der Schlagschälfestigkeit (impact peel energy) angefertigt. Dabei die Prüfkörper zum Aushärten der Ktebstoffmischung für 30 Minuten bei 180°C im Umlufttrockenschrank ausgehärtet. Die Messergebnisse der Zugscherfestigkeit bei Raumtemperatur sowie der Schlagschälfestigkeit nach ISO 11343 bei Raumtemperatur und -30°C sind in der nachfolgenden Tabelle aufgeführt:
Aus den Zugscherfestigkeiten und den Schlagschälarbeiten der vorstehenden Tabelle ist deutlich ersichtlich, dass die erfindungsgemäßen Klebstoffzusammensetzungen auf Basis flüssiger Kautschuke gegenüber vergleichbaren Kautschukzusammensetzungen des Standes der Technik sowohl höhere Zugscherfestigkeiten als auch deutlich höhere Schlagschälarbeiten gewährleisten, insbesondere bei Raumtemperatur aber auch bei tiefen Temperaturen bis zu -30°C. Diese höheren Schlagschälarbeiten sind ein wesentliches Kriterium für den Fahrzeugbau, da derartige Klebungen im Falle einer stoßartigen Belastung bei Unfällen sehr viel mehr Energie aufnehmen können.From the tensile shear strengths and the impact peeling work of the above table, it can be clearly seen that the adhesive compositions based on liquid rubbers according to the prior art provide both higher tensile shear strengths and significantly higher impact peel strength compared to comparable rubber compositions, especially at room temperature but also at low temperatures up to -30 ° C. This higher impact peeling is an essential criterion for vehicle construction, since such bonds can absorb much more energy in the event of a shock load in accidents.
Claims (11)
- A single-component, high-temperature-curing reactive composition based on natural and/or synthetic elastomers containing olefinic double bonds and on vulcanizing agents, wherein it containsa) at least one liquid polyene having a molecular weight between 400 and 80,000, by preference between 800 and 25,000;b) at least one liquid polybutadiene having 10-20% vinyl-1,2, 50-60% trans-1,4, 25-35% cis-1,4 double bonds as a microstructure; andc) a vulcanizing system of sulfur and accelerators and/or, if applicable, quinone oximes.
- The single-component, high-temperature-curing reactive composition according to Claim 1, having an additional content of at least one solid rubber from the group of cis-1,4-polybutadiene, styrene-butadiene rubber, synthetic isoprene rubber, natural rubber, ethylene-propylene-diene rubber (EPDM), polycyclooctenamer, nitrile rubber, butyl rubber, acrylic rubber, or polychloroprene.
- The single-component, high-temperature-curing reactive composition according to at least one of the preceding claims, wherein the liquid polybutadiene b) has a molecular weight (Mn) between 2,000 and 12,000, by preference between 5,000 and 9,000.
- The single-component, high-temperature-curing reactive composition according to at least one of the preceding claims, having an additional content of at least one thermoplastic polymer powder.
- The high-temperature-curing composition according to at least one of the preceding claims, wherein a vulcanizing system of sulfur, organic vulcanization accelerators, and zinc compounds is used for curing.
- The high-temperature-curing composition according to at least one of the preceding claims, wherein the vulcanizing system consists of 4 wt% to 25 wt%, by preference 5 wt% to 15 wt%, powdered sulfur, 0.25 wt% to 8 wt%, by preference 0.4 wt% to 6 wt%, organic accelerator, and 0.5 wt% to 10 wt%, by preference 2 wt% to 8 wt%, zinc compounds, by preference zinc oxide, the wt% being based on the total composition.
- The high-temperature-curing composition according to at least one of the preceding claims, wherein the vulcanizing system additionally contains 0 to 2 wt% of a bifunctional vulcanization crosslinker.
- The high-temperature-curing composition according to Claim 7, wherein bifunctional dithiocarbamates, in particular 1,6-bis(N,N-dibenzylthiocarbamoyldithio)hexane, is used as a bifunctional vulcanization crosslinker.
- The composition according to at least one of the preceding claims, wherein it additionally contains fillers, rheology adjuvants, extender oils, blowing agents, pigments, adhesion promoters, and/or aging protection agents.
- The composition according to at least one of the preceding claims, containing- solid rubber: 0 - 15 wt%, by preference 0-12 wt%;- liquid polybutadiene with 10-20% vinyl-1,2, 50-60% trans-1,4, and 25-35% cis-1,4 double bonds: 2 - 50 wt%, by preference 5 - 42 wt%;- polybutadiene having carboxyl groups: 0 - 25 wt%, by preference 1 - 15 wt%;- sulfur: 4 - 25 wt%, by preference 5 - 15 wt%;- accelerator: 0.25 - 8.0 wt%, by preference 0.4 - 6 wt%;- bifunctional vulcanization crosslinker: 0 - 2 wt%, by preference 0 - 1 wt%;- zinc oxide: 0.5 - 10 wt%, by preference 2-8 wt%;- phenol resin: 0 - 8 wt%, by preference 0 - 6 wt%;- disodium salt of hexamethylene-1,6-bis(thiosulfate): 0 - 2.5 wt%, by preference 0.1 - 1.8 wt%;- antioxidant: 0 - 2 wt%, by preference 0.1 - 1.0 wt%;- calcium oxide: 0 - 8 wt%, by preference 1 - 6 wt%;- carbon black: 0 - 4 wt%, by preference 0.1-2 wt%;- calcium carbonate, uncoated: 10-45 wt%, by preference 15-40 wt%;- calcium carbonate, coated: 0-30 wt%, by preference 5-18 wt%,the sum of the constituents of the composition adding up to 100%.
- Use of the composition according to at least one of the preceding claims as a single-component adhesive, sealant, or coating compound in automobile body manufacture.
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| PCT/EP2007/000728 WO2007118529A1 (en) | 2006-04-06 | 2007-01-29 | Bonding agents and sealants based on liquid rubbers |
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| EP0338985B1 (en) | 1988-04-18 | 1994-05-18 | Ciba-Geigy Ag | Modified epoxy resins |
| DE3834818C1 (en) * | 1988-10-13 | 1989-11-09 | Teroson Gmbh, 6900 Heidelberg, De | |
| DE3835740A1 (en) * | 1988-10-20 | 1990-05-10 | Henkel Kgaa | HOT VOLCANIZABLE ADHESIVES AND THEIR USE IN METHODS FOR THE FLAT CONNECTION OF SOLID BODY SURFACES |
| SE9200704L (en) | 1992-03-06 | 1993-09-07 | Casco Nobel Ind Prod | Thermoplastic microspheres, process for their preparation and use of the microspheres |
| US6361643B2 (en) * | 1994-11-23 | 2002-03-26 | Henkel Teroson Gmbh | Method for reducing mechanical vibration in metal constructions |
| DE19502381A1 (en) | 1995-01-26 | 1996-08-01 | Teroson Gmbh | Structural raw rubber-based adhesives |
| DE19730425A1 (en) | 1997-07-16 | 1999-01-21 | Henkel Teroson Gmbh | Heat-curing laundry-resistant shell sealant |
| JP2000319475A (en) | 1999-03-08 | 2000-11-21 | Mitsubishi Rayon Co Ltd | Impact resistant resin composition, manufacture thereof and molded item thereof |
| JP2000313786A (en) | 1999-04-28 | 2000-11-14 | Mitsubishi Rayon Co Ltd | Impact resistant acrylic resin composition, its production and molded article |
| CA2405584A1 (en) | 2000-04-10 | 2002-10-08 | Henkel Kommanditgesellschaft Auf Aktien | Impact-resistant epoxy resin compositions |
| DE10062860A1 (en) * | 2000-12-16 | 2002-06-27 | Henkel Teroson Gmbh | Rubber compositions with plastisol-like flow behavior |
| DE10062861A1 (en) | 2000-12-16 | 2002-06-27 | Henkel Teroson Gmbh | Odor-reduced sulfur-crosslinking rubber compounds |
| EP1239016A1 (en) | 2001-03-08 | 2002-09-11 | Sika AG, vorm. Kaspar Winkler & Co. | Elastic meth (acrylic) adhesive compositions |
| DE10163252A1 (en) * | 2001-12-21 | 2003-07-10 | Henkel Teroson Gmbh | Surface stiffening rubber systems |
-
2006
- 2006-04-06 DE DE102006016577A patent/DE102006016577A1/en not_active Withdrawn
-
2007
- 2007-01-29 ES ES07711401T patent/ES2335546T3/en active Active
- 2007-01-29 JP JP2009503433A patent/JP2009532537A/en not_active Withdrawn
- 2007-01-29 CN CN200780011096XA patent/CN101410448B/en not_active Expired - Fee Related
- 2007-01-29 AT AT07711401T patent/ATE449817T1/en active
- 2007-01-29 WO PCT/EP2007/000728 patent/WO2007118529A1/en active Application Filing
- 2007-01-29 KR KR1020087024350A patent/KR20090006081A/en not_active Application Discontinuation
- 2007-01-29 DE DE502007002108T patent/DE502007002108D1/de active Active
- 2007-01-29 EP EP07711401A patent/EP2001952B1/en active Active
-
2008
- 2008-07-31 US US12/183,644 patent/US7902298B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101410448B (en) | 2011-12-21 |
| US7902298B2 (en) | 2011-03-08 |
| DE102006016577A1 (en) | 2007-10-11 |
| ATE449817T1 (en) | 2009-12-15 |
| US20090036595A1 (en) | 2009-02-05 |
| KR20090006081A (en) | 2009-01-14 |
| WO2007118529A1 (en) | 2007-10-25 |
| ES2335546T3 (en) | 2010-03-29 |
| JP2009532537A (en) | 2009-09-10 |
| CN101410448A (en) | 2009-04-15 |
| EP2001952A1 (en) | 2008-12-17 |
| DE502007002108D1 (en) | 2010-01-07 |
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